EP1767994B1 - Précurseur de plaque d'impression planographique - Google Patents

Précurseur de plaque d'impression planographique Download PDF

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Publication number
EP1767994B1
EP1767994B1 EP06020269A EP06020269A EP1767994B1 EP 1767994 B1 EP1767994 B1 EP 1767994B1 EP 06020269 A EP06020269 A EP 06020269A EP 06020269 A EP06020269 A EP 06020269A EP 1767994 B1 EP1767994 B1 EP 1767994B1
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EP
European Patent Office
Prior art keywords
group
protective layer
printing plate
planographic printing
plate precursor
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Application number
EP06020269A
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German (de)
English (en)
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EP1767994A2 (fr
EP1767994A3 (fr
Inventor
Shigeo c/o Fuji Photo Film Co. Ltd. Koizumi
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Fujifilm Corp
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Fujifilm Corp
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Publication of EP1767994A3 publication Critical patent/EP1767994A3/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/12—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by non-macromolecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • the present invention relates to a negative-type planographic printing plate precursor which can be directly delineated with infrared laser light and from which a plate can be made rapidly.
  • a PS plate having a structure in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used.
  • a desired printing plate is obtained by dissolving and removing a non-image part after mask exposure via a lith film (plane exposure).
  • the digitalizing technique of electronically processing, storing and outputting image information using a computer has become widespread. And, various new image outputting methods corresponding to such digitalizing techniques have been put to practical use.
  • CTP Computer To Plate
  • planographic printing plate precursor which can be scanned and exposed
  • a structure in which a lipophilic photosensitive resin layer (hereinafter, also referred to as "photosensitive layer") containing a photosensitive compound capable of generating active species such as radical and Br ⁇ nsted acid by laser exposure is provided on a hydrophilic support has been proposed.
  • a negative-type planographic printing plate can be obtained by scanning this planographic printing plate precursor based on digital information to generate an active species, causing a physical or chemical change on a photosensitive layer by its action to insolubilize this, followed by developing treatment.
  • a planographic printing plate precursor in which a photopolymerization-type photosensitive layer containing a photopolymerization initiator excellent in photosensitive speed, an addition-polymerizable ethylenic unsaturated compound, and a binder polymer soluble in an alkali developer and, if necessary, an oxygen-shielding protective layer are provided on a hydrophilic support (e.g. see Japanese Patent Application Laid-Open ( JP-A) No. 10-228109 ) has advantages in that the precursor is excellent in productivity, is simple in developing treatment, and has better resolution and inking property, and therefore, has desirable printing performance.
  • JP-A Japanese Patent Application Laid-Open
  • a method of providing a protective layer containing a water-soluble polymer on a photosensitive layer is known.
  • a protective layer By the presence of a protective layer, polymerization inhibition is prevented, a reaction of curing a photosensitive layer is promoted, and it becomes possible to improve the strength of an image part.
  • safety light fog refers to in visible light photosensitive material
  • a method of providing a protective layer containing at least one kind of polyvinylpyrrolidone and a copolymer of vinylpyrrolidone and vinyl acetate, and having a controlled film weight of 0.5 g/m 2 to 2.30 g/m 2 is known.
  • a protective layer containing a polyvinylpyrrolidone-based polymer has a problem in that when hygroscopicity is increased, this increases dependency of oxygen permeability of a protective layer on humidity, and when humidity is increased during storage, adhesion between a protective layer surface and an adjacent set-off sheet or a plate material back occurs.
  • a polyvinylpyrrolidone-based polymer easily remains on a photosensitive layer surface having a hydrophobic surface at an image part after developing treatment and, when developing treatment is performed for a long time using an automatic developing machine, polyvinylpyrrolidone remains on a photosensitive layer surface in some cases.
  • a problem of considerable decrease in inking property at an image part occurs.
  • planographic printing plate precursor which is a photopolymerization planographic printing plate precursor having an oxygen-permeable protective layer suppressing polymerization inhibition of a photosensitive layer, having little dark polymerization at storage with time, and not causing safe light fog due to illumination light during plate-making and, as described above, not causing a problem of adhesion of a protective layer surface under high humidity storage conditions, and a problem such as reduction in inking property.
  • US-A-5 997 993 and US-A-5 677 110 discloses planographic printing of plate having a protective layer containing PVA and a copolymer of ethylene oxide and propylene oxide.
  • EP-A-1 552 923 discloses a lithographic printing plate precursor having a protective layer containing PVA.
  • An object of the present invention is to solve the conventional problems, and attain the above object.
  • an object of the invention is to provide a planographic printing plate precursor which can be written with an infrared laser, and has a protective layer, and can improve productivity in plate-making work.
  • an object of the invention is to provide a planographic printing plate precursor provided with a protective layer which suppresses polymerization inhibition of a photosensitive layer, moreover, does not cause fog at long term storage and safe light fog, is excellent in development removability, further, suppresses adhesion between a surface of a protective layer of a planographic printing plate precursor and an adjacent set-off sheet or a surface on a support side of a planographic printing plate precursor even when planographic printing plate precursors are stacked, and is better in inking property even at long term treatment with an automatic developing machine, on a photosensitive layer which can be written with an infrared laser.
  • an object of the invention to provide a planographic printing plate precursor with a protective layer which improves a rubbing flaw.
  • a planographic printing plate precursor in which a photosensitive layer and a protective layer are successively laminated on a surface of an aluminum support exhibiting hydrophilicity, characterized in that the protective layer contains a binder polymer, and a copolymer of ethylene oxide and propylene oxide is provided.
  • a protective layer contain polyvinyl alcohol having a defined range of a saponification degree, and a copolymer of ethylene oxide and propylene oxide, the above objects can be attained, which resulted in completion of the invention.
  • planographic printing plate precursor of the present invention is a planographic printing plate precursor as claimed in claim 1.
  • laminated on a support in this order means that a photosensitive layer and a protective layer are arranged on a support in this order, but this phrase does not deny the presence of other layers (for example, an intermediate layer, a back coat layer, etc.) arranged in accordance with specific objectives.
  • the binder polymer contained in the protective layer is a polyvinyl alcohol having a saponification degree of 91 mole% or more.
  • the content of the polyvinyl alcohol having a saponification degree of 91 mol% or more is 45 to 95 % by mass relative to a total solid matter amount of a protective layer.
  • a content of ethylene oxide contained in a copolymer of ethylene oxide and propylene oxide contained in the protective layer is 30 to 80 % by mass.
  • oxygen permeability of a protective layer under environment of 25°C, 60 %RH and 1 atm is 0.5 ml/m 2 ⁇ day or more and 100 ml/m 2 ⁇ day or less.
  • the photosensitive layer contains an infrared absorbing agent, a polymerization initiator, a polymerizable compound and a binder polymer
  • the binder polymer is a binder polymer having a repetition unit represented by the following formula (i).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a tethering group containing 2 or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and having the number of those atoms of 2 to 82
  • A represents an oxygen atom or -NR 3 -
  • R 3 represents a hydrogen atom or a monovalent hydrocarbon group of a carbon number of 1 to 10
  • n represents an integer of 1 to 5
  • a protective layer in the invention contains a binder polymer, and a copolymer of ethylene oxide and propylene oxide, a film strength is improved, and a surface of low adherability is formed. Further, this protective layer has proper oxygen permeability.
  • planographic printing plate precursors having this protective layer are laminated, it is presumed that, adhesion between a protective layer constituting a surface on a photosensitive layer side of a planographic printing plate precursor, and an adjacent set-off sheet or a surface on a support side of a planographic printing plate precursor is suppressed, and a rubbing flaw generated between a protective layer surface and an aluminum support back, and a flaw of a protective layer due to a trash and a sand particle can be suppressed and, at the same time, storing property with time and safe light suitability are excellent, and occurrence of deteriorated inking can be suppressed.
  • a planographic printing plate precursor which can be written with an infrared laser, has better inking property, and has a protective layer excellent in flaw resistance can be provided.
  • a planographic printing plate precursor provided with a protecting layer which suppresses polymerization inhibition of a photosensitive layer is better in safe light suitability and storing property with time, is excellent in development removability and inking property, further, suppresses adhesion between a surface of a protective layer of a planographic printing plate precursor and an adjacent set-off sheet or a surface on a support side of a planographic printing plate precursor even when planographic printing plate precursors are stacked, and can improve a rubbing flaw generated between a protective layer surface and an aluminum support back, and a flaw of a protective layer due to a trash and a sand particle, on a photosensitive layer which can be written with a laser, is provided.
  • the planographic printing plate precursor of the invention is a planographic printing plate precursor in which a photosensitive layer containing an infrared absorbing agent, a polymerization initiator, a polymerizable compound and a binder polymer, and a protective layer are successively laminated on a surface of an aluminum support exhibiting hydrophilicity, the protective layer is as defined in claim 1.
  • the protective layer in the invention is characterized in that the layer contains polyvinyl alcohol having a saponification degree of 91 mol% or more (hereinafter, conveniently, referred to as "specified polyvinyl alcohol”), and a copolymer of ethylene oxide and propylene oxide.
  • a photosensitive layer is a polymerizable negative-type photosensitive layer (described later)
  • a protective layer is disposed on the photosensitive layer for the purpose of preventing mixing in of a low-molecular compound such as oxygen, moisture, and basic substance present in the air which inhibits an image forming reaction, into the photosensitive layer, usually for performing light exposure in the air.
  • a protective layer disposed for such the purpose contain specified polyvinyl alcohol, and a copolymer of ethylene oxide and propylene oxide, it becomes possible to optimally control oxygen permeability, and improvement in a sensitivity, improvement in storing property with time, and improvement in safe light suitability can be attained without reducing inking property. Also, an excellent film strength can be attained. As a result, a protective layer can attain not only the aforementioned improvement in sensitivity, but also improvement in storing property with time, and improvement in safe light suitability without reducing inking property, and has become possible to suppress deterioration due to deformation and occurrence of a flaw.
  • planographic printing plate precursors of the invention when planographic printing plate precursors of the invention are stacked, it becomes possible to suppress adhesion between a set-off sheet or a surface of a protective layer of a planographic printing plate precursor and an adjacent back of a support of a planographic printing plate precursor.
  • fundamental property desired on a protective layer disposed on a polymerizable negative-type photosensitive layer is that permeation of light used in exposure is not substantially inhibited, suitable oxygen permeability is possessed, and adherability with a photosensitive layer is excellent, but its surface is low adhering, and can be easily removed in a developing step after exposure.
  • the invention is characterized in that, as a binder component of a protective layer, polyvinyl alcohol having a saponification degree of 91 mol% or more (specified polyvinyl alcohol) is used.
  • This specified polyvinyl alcohol has a surface excellent in film forming property and having relatively low adherability.
  • Polyvinyl alcohol having a saponification degree of 91 mol% or more used in the invention may be such that a part of it may be substituted with ester, ether or acetal, or a part of it may be modified and, further, similarly, a part of it may have other copolymerization component, as far as it has an unsubstituted vinyl alcohol unit for having necessary oxygen shielding property and low adhering surface if a saponification degree is in the above range.
  • a saponification degree of PVA used is higher (as a content of an unsubstituted vinyl alcohol unit in a protective layer is higher), oxygen shielding property becomes higher, and this is advantageous in a sensitivity.
  • a protective layer in the invention for example, by using a mica compound described later together with polyvinyl alcohol having a saponification degree of 91 mol% or more, a film strength of a protective layer is further improved, and flaw resistance and oxygen shielding property can be enhanced.
  • such the specified polyvinyl alcohol has a polymerization degree in a range of 200 to 2400.
  • examples include PVA-102, PVA-103, PVA-104, PVA-105, PVA-110, PVA-117, PVA-120, PVA-124, PVA-117H, PVA-135H, PVA-HC, PVA-617, PVA-624, PVA-706, PVA-613, PVA-CS, and PVA-CST manufactured by Kuraray Co., Ltd., Gosenol NL-O5, NM-11, NM-14, AL-06, P-610, C-500, A-300, and AH-17 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and JF-04, JF-05, JF-10, JF-17, JF-17L, JM-05, JM-10, JM-17, JM-17L, JT-05, JT-13, and JT-15 manufactured by Japan Vam & Poval Co., Ltd.
  • Examples of specified polyvinyl alcohol in the invention include carboxy-modified polyvinyl alcohol such as itaconic acid or maleic acid-modified polyvinyl alcohol, and sulfonic acid-modified polyvinyl alcohol as a preferable example as far as it has a saponification degree of 91 mol% or more.
  • acid-modified polyvinyl alcohol suitable as such the specified polyvinyl alcohol include KL-118, KM-618, KM-118, SK-5102, MP-102, and R-2105 manufactured by Kuraray Co., Ltd., Gosenal CKS-50, T-HS-1, T-215, T-350, T-330, and T-330H manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and AF-17, and AT-17 manufactured by Japan Vam & Poval Co., Ltd.
  • the specified polyvinyl alcohol is contained at preferably in a range of 45 to 95 % by mass, more preferably in a range of 50 to 90 % by mass relative to a total solid matter amount in a protective layer.
  • content is less than 45 % by mass, film forming property is insufficient, and a sensitivity is reduced and, when the content exceeds 95 % by mass, the effect of suppressing adhesion between stacked planographic printing plate precursors is manifested with difficulty.
  • the specified polyvinyl alcohol at least one kind may be used, or a plurality of the specified polyvinyl alcohols may be used. Also when a plurality of kinds of specified polyvinyl alcohols are used together, an amount of a sum thereof is preferably in the aforementioned mass range.
  • the copolymer of ethylene oxide and propylene oxide in the invention functions as an oxygen permeation controlling agent for a protective layer.
  • Specified polyvinyl alcohol which is a main component constituting a protective layer in the invention has a high saponification degree (91 mol% or more), and has low oxygen permeability. For this reason, flaw resistance, and adhesion resistance are very excellent but there is a problem of increase in fog at storage with time, and deterioration in safe light suitability, accompanying with low oxygen permeability.
  • a copolymer of ethylene oxide and propylene oxide is added to such the protective layer, excellent flaw resistance can be obtained and, at the same time, oxygen permeability can be improved without deteriorating property of adhesion resistance.
  • polyvinyl alcohol forms an excellent oxygen shielding film by hydrogen bond between -OH groups contained in the polyvinyl alcohol. Therefore, as a simplest method of improving oxygen permeability of a polyvinyl alcohol film, a method of using polyvinyl alcohol having a small content of an -OH group, having a high copolymerization ratio of a vinyl acetate group which is a large side chain inhibiting crystallization, and having a low saponification degree is contemplated.
  • a method of adding a plasticizer to a polyvinyl alcohol material is known.
  • a well-known plasticizer of polyvinyl alcohol include glycerin, diethylene glycol, triethylene glycol, propylene glycol, 2,3-butanediol, 1,3-butanediol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and trimethylolpropane.
  • glycerin diethylene glycol, triethylene glycol, propylene glycol, 2,3-butanediol, 1,3-butanediol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and trimethylolpropane.
  • polyvinylpyrrolidone As such the water-soluble polymer, polyvinylpyrrolidone, polyethylene glycol, soluble starch, carboxymethylcellulose, and hydroxyethylcellulose are known. Among them, since polyvinylpyrrolidone has a pyrrolidone group having a large volume on a side chain, the effect of inhibiting crystallization of polyvinyl alcohol is great.
  • a protective layer containing a polyvinylpyrrolidone-based polymer has increased hygroscopicity, increases dependency of oxygen permeability of a protective layer on a humidity and, when a humidity is increased at storage, adhesion is caused between a protective layer surface and an adjacent set-off sheet or a printing material back.
  • a polyvinylpyrrolidone-based polymer easily remains on a surface of a photosensitive layer having a hydrophobic surface at an image part after developing treatment and, when long term developing treatment is performed using an automatic developing machine, polyvinylpyrrolidone remains on a surface of a photosensitive layer in some cases.
  • the present inventors confirmed of addition of various water-soluble polymers and oligomers, and found out that by further adding a copolymer of ethylene oxide and propylene oxide to a protective layer containing polyvinyl alcohol having a saponification degree of 91 mol% or more, excellent flaw resistance can be obtained and, at the same time, oxygen permeability can be improved at a small addition amount without deteriorating property of adhesion resistance, which resulted in completion of the invention.
  • the copolymer of ethylene oxide and propylene oxide used in the invention is preferably a compound represented by the formula: HO-(CH 2 CH 2 O) a (C 3 H 6 O) b (CH 2 CH 2 O) c -H.
  • a, b and c represent an integer of 1 or more, and it is further preferable that a molecular weight of the compound represented by the formula is in a range of 2,000 to 27,000.
  • examples include polyether-type polymer nonionic surfactants manufactured by USA Wine dot (Pluronic series), Pluronic series (ethylene oxide/propylene oxide copolymers; Pluronic P-84, L-64, P-85, F-88, P-94, P-75, P-65, F-77) manufactured by ADEKA CORPORATION.
  • Such the Pluronics function as a surfactant, an ethylene oxide part is a hydrophilic group, and a propylene oxide part is a hydrophilic group, and their property can be freely regulated by a molecular weight of a propylene oxide part and an addition amount of ethylene oxide.
  • a copolymer suitably used as a copolymer of ethylene oxide and propylene oxide contained in a protective layer of the planographic printing plate precursor of the invention is such that a content of ethylene oxide contained in the copolymer of ethylene oxide and propylene oxide is 30 % by mass or more, preferably in a range of 30 % by mass or more and 80 % by mass or less, further preferably in a range of 30 % by mass or more and 60 % by mass or less.
  • a weight average molecular weight of polypropylene oxide is preferably in a range of 950 or more and 3,250 or less, more preferably in a range of 1,200 or more and 3,250 or less.
  • An amount of a copolymer of ethylene oxide and propylene oxide contained in a protective layer of the planographic printing plate precursor of the invention is from 2.0 % to 15 % by mass relative to the total solid matter amount of a protective layer.
  • Components of a protective layer selection of specified polyvinyl alcohol and a copolymer of ethylene oxide and propylene oxide, use of an additive
  • a coating amount are selected in view of oxygen shielding property, development removality, fog property, adherability, and flaw resistance.
  • the protective layer in the invention has oxygen permeability at 25°C, 60 %RH and 1 atm of 0.5 ml/m 2 ⁇ day or more and, in order to attain this oxygen permeability, it is preferable to use a procedure of adjusting components of the protective layer, and a coating amount.
  • adherability with an image part of a photosensitive layer, and uniformity of a film are also extremely important from a viewpoint of handling of a plate. That is, when a hydrophilic layer comprising a water-soluble polymer is laminated on a lipophilic photosensitive layer, film peeling easily occurs due to lack of an adhering force, and a peeled part causes a defect such as deteriorated film curing due to polymerization inhibition of oxygen. In response to this, in order to improve adherability between these two layers, there are many proposals.
  • US 4,072,527 and US 4,072,528 describe that sufficient adherability is obtained by mixing 20 to 60 % by mass of an acryl-based emulsion or a water-insoluble vinyl ester-vinyl acetate copolymer into a hydrophilic polymer containing mainly polyvinyl alcohol, and laminating this on a photosensitive layer.
  • Colorants which have high transmittance for light (infrared light in the invention) used to expose the photosensitive layer and can absorb the light having wavelengths which are not involved in exposure may be added in the protective layer according to the invention.
  • the protective layer can be thereby improved in safe-light adaptability.
  • the protective layer in the invention is formed by coating a coating solution for a protective layer obtained by blending the specified polyvinyl alcohol, and a binder component (or an aqueous solution in which a binder component containing specified polyvinyl alcohol is dissolved) containing a copolymer of ethylene oxide and propylene oxide on a photosensitive layer.
  • Known additives such as surfactants improving coatability and water-soluble plasticizers improving the properties of the coating film may be added to this protective layer coating solution.
  • the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin and sorbitol.
  • a water-soluble (meth)acrylic polymer may also be added.
  • known additives that improve adhesion to the photosensitive layer and the stability of the coating solution with time may be added to this coating solution.
  • a coating amount of the protective layer in the invention is from 0.3 g/m 2 to 3.0 g/m 2 .
  • the amount is less than 0.1 g/m 2 , a film strength of a protective layer cannot be maintained, and flaw resistance is deteriorated in some cases.
  • the amount exceeds 3.0 g/m 2 , scattering of light introduced into a protective layer due to light exposure is generated, deterioration in image quality is caused, oxygen permeability is decreased too much, and safe light suitability is deteriorated in some cases.
  • the photosensitive layer of the planographic printing plate precursor according to the invention is a polymerizable negative type photosensitive layer containing an infrared absorber, a polymerization initiator, a polymerizable compound and a binder polymer as essential components, and as required, colorants and other optional components.
  • the polymerizable negative type photosensitive layer in the invention is sensitive to infrared light and is therefore photosensitive to an infrared laser useful for CTP.
  • the infrared absorber contained in the photosensitive layer is put into an electronically excited state by infrared laser radiation (exposure) highly sensibly.
  • Electronic transfer, energy transfer and heat generation (light-heat conversion function) relating to this electronically excited state act on the polymerization initiator coexisting in the photosensitive layer to cause a chemical change of the polymerization initiator to generate radicals.
  • radical-generation mechanisms include (1) a mechanism in which the heat generated by the light-heat conversion function of an infrared absorber thermally decomposes a polymerization initiator (e.g., a sulfonium salt) which will be explained later to generate radicals, (2) a mechanism in which excited electrons generated from an infrared absorber transfer to a polymerization initiator (e.g., an activated halogen compound) to generate radicals and (3) a mechanism in which electrons generated from a polymerization initiator (e.g., a borate compound) transfer to an excited infrared absorber to generate radicals. Then, a polymerizable compound is allowed to enter into a polymerization reaction by the generated radicals to cure the exposed portion, forming an image area.
  • a polymerization initiator e.g., a sulfonium salt
  • the photosensitive layer contains the infrared absorber in the planographic printing plate precursor of the invention and the planographic printing plate precursor is therefore particularly suitable to plate-making in which an image is formed directly by an infrared laser having a wavelength of 750 nm to 1400 nm.
  • the planographic printing plate precursor of the invention can develop higher image forming characteristics than conventional planographic printing plate precursors.
  • the photosensitive layer according to the invention contains an infrared absorber in order to develop an energy transfer function and a light-heat conversion function.
  • the infrared absorber is put into an electronic excited state highly sensibly by infrared laser radiation (exposure) and electronic transfer, energy transfer and heat generation (light-heat conversion function) relating to this electronically excited state act on the initiator which will be described later to cause a chemical change of the polymerization initiator to generate radicals.
  • the infrared absorber used in the invention is preferably a dye or a pigment having an absorption maximum at a wavelength in the range of 750 nm to 1400 nm.
  • the dye may be any known commercial dye including those described in publications such as Senryo Binran (Dye Handbook) (published in 1970 and compiled by the Society of Synthetic Organic Chemistry, Japan ).
  • Examples of such dyes include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.
  • Preferable dyes include cyanine dyes such as those described in patent documents such as JP-A Nos. 58-125246 , 59-84356 , 59-202829 , and 60-78787 , and the methine dyes described in JP-A Nos. 58-173696 , 58-181690 , 58-194595 , etc. Further, the naphthoquinone dyes described in JP-A Nos. 58-112793 , 58-224793 , 59-48187 , 59-73996 , 60-52940 , 60-63744 , etc., the squarylium dyes described in JP-A No. 58-112792 , etc., and the cyanine dyes described in Britsh Patent No. 434,875 are also preferably used.
  • a near infrared absorbing sensitizer described in USP No. 5,156,938 is also preferably used, and a substitute arylbenzo(thio)pyrylium salt described in USP No. 3,881,924 , a trimethinethiapyrylium salt described in JP-A No. 57-142645 ( USP No. 4,327,169 ), a pyrylium-based compound described in JP-A Nos. 58-181051 , 58-220143 , 59-41363 , 59-84248 , 59-84249 , 59-146063 , and 59-146061 , a cyanine pigment described in JP-A No.
  • 59-216146 a pentamethinethiopyrylium salt described in USA No. 4,283,475 , and a pyrylium compound disclosed in JP-B Nos. 5,13514 , and 5-19702 are also preferably used.
  • Another preferable examples of a dye include near infrared absorbing dyes described as the formulas (I) and (II) in USP No. 4,756,993 .
  • an infrared absorbing pigment in the invention include particular indoleninecyanine pigments described in JP-A No. 2002-278057 as exemplified below.
  • dyes particularly preferable among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickelthiolate complexes and indolenine cyanine dyes.
  • the dyes are more preferably cyanine dyes and indolenine cyanine dyes, still more preferably cyanine dyes represented by the formula (a).
  • X 1 represents a hydrogen atom, a halogen atom, -NPh 2 , X 2 -L 1 or a group shown below.
  • X 2 represents an oxygen atom, a nitrogen atom or a sulfur atom
  • L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a heteroatom, and a hydrocarbon group having 1 to 12 carbon atoms containing a heteroatom.
  • the heteroatom refers to N, S, O, halogen atom or Se.
  • Xa - has the same meaning as that of Za - defined later, and R a represents a substituent group selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.
  • R 1 and R 2 independently represent a hydrocarbon group having 1 to 12 carbon atoms.
  • each of R 1 and R 2 is preferably a hydrocarbon group having 2 or more carbon atoms, and more preferably R 1 and R 2 are linked to each other to form a 5- or 6-memberred ring.
  • Ar 1 and Ar 2 may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent group.
  • the aromatic hydrocarbon group is preferably a benzene ring or a naphthalene ring.
  • the substituent group is preferably a hydrocarbon group having 12 or less carbon atoms, a halogen atom or an alkoxy group having 12 or less carbon atoms.
  • Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkyl methylene group having 12 or less carbon atoms.
  • R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent group.
  • the substituent group is preferably an alkoxy group having 12 or less carbon atoms, a carboxyl group or a sulfo group.
  • R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms.
  • Each of R 5 , R 6 , R 7 and R 8 is preferably a hydrogen atom because the starting material is easily available.
  • Za - represents a counter anion. However, when the cyanine dye represented by the formula (a) has an anionic substituent group in its structure and does not necessitate neutralization of the charge, Za - is not necessary.
  • Za - is preferably a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion or a sulfonate ion, particularly preferably a perchlorate ion, a hexafluorophosphate ion or an aryl sulfonate ion.
  • Examples of the cyanine dyes represented by the formula (a), which can be preferably used in the present invention, include those described in columns [0017] to [0019] in JP-A No. 2001-133969 .
  • infrared absorbing agent in the present invention include specific indolenine cyanine dyes described in Japanese Patent Application Nos. 2001-6326 and 2001-237840 supra.
  • the cyanine dyes represented by formula (a) is particularly preferably a dye which does not contain a halogen ion as a counter ion.
  • the pigment includes commercially available pigments and those described in the Color Index (C. I.) Handbook, Saishin Ganryo Binran (Latest Dye Handbook) (published in 1977 and compiled by the Japanese Society of Pigment Technology ); Saishin Ganryho Oyo Gijyutsu (Latest Pigment Applied Technology) (published in 1986 by CMC Publishing Co., Ltd. ); and Insatsu Inki Gijyutsu (Printing Ink Technology) (published in 1984 by CMC Publishing Co., Ltd. ).
  • C. I. Color Index
  • Saishin Ganryo Binran Latest Dye Handbook
  • Saishin Ganryho Oyo Gijyutsu Latest Pigment Applied Technology
  • Insatsu Inki Gijyutsu Print Ink Technology
  • the pigment examples include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, violet pigments, blue pigments, green pigments, fluorescent pigments, metallic powder pigments, and other pigments such as polymer-binding dyes.
  • preferable pigments include insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine type pigments, anthraquinone type pigments, perylene and perinone type pigments, thioindigo type pigments, quinacridone type pigments, dioxazine type pigments, isoindolinone type pigments, quinophthalone type pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, and carbon black, which is preferable among these.
  • the pigments may or may not be subjected to surface treatment.
  • Methods of surface treatment include coating the surface with resin or wax; allowing a surfactant to adhere to the surface; and bonding a reactive material (e.g., a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) onto the surface of the pigment.
  • a reactive material e.g., a silane coupling agent, an epoxy compound, a polyisocyanate, etc.
  • the particle diameters of the pigments are in the range of preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 1 ⁇ m, most preferably 0.1 to 1 ⁇ m. When the particle diameters are in the preferable range, dispersion stability of the pigments in the coating solution and uniformity of the photosensitive layer can be achieved.
  • dispersing machines used widely in production of inks or toners and dispersing techniques can be suitably selected.
  • suitable dispersing machines include a supersonic dispersing device, sand mill, attritor, pearl mill, super mill, ball mill, impeller, disperser, KD mill, colloid mill, dynatron, triple roll mill, press kneader, etc. These are described in detail in the aforementioned Saishin Ganryho Oyo Gijyutsu (Latest Newest Pigment Applied Technology) (published in 1986 by CMC Publishing Co., Ltd. ).
  • the aforementioned infrared absorbing agents may be added to the same layer or to a separately provided layer in the photosensitive layer of the invention.
  • These infrared absorbing agents can be added in a ratio of 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and as the infrared absorbing agent, the dye can be added in the range of 0.5 to 10% by mass, and the pigment can be added in the range of 0.1 to 10% by mass, based on a total solid content in the photosensitive layer, from the viewpoint of uniformity and durability of the photosensitive layer.
  • any compound may be used as the polymerization initiator used in the invention insofar as it has the abilities to initiate and to progress a reaction for curing a polymerizable compound which will be explained later and generates radicals by supplying energy: examples of these compounds include thermally decomposable radical generators which are decomposed by heat to generate radicals, electron transfer type radical generators which receive excited electrons of an infrared absorber to generate radicals or electron transfer type radical generators whose electrons transfer to an excited infrared absorber to generate radicals. Examples of these compounds include onium salts, activated halogen compounds, oxime ester compounds and borate compounds. Two or more of these compounds may be used together. In the invention, onium salts are preferable and among the onium salts, sulfonium salts are particularly preferable.
  • the sulfonium salt polymerization initiator used preferably in the present invention includes onium salts represented by the following formula (1).
  • R 11 , R 12 and R 13 each independently represent a hydrocarbon group having 20 or less carbon atoms, which may have a substituent group.
  • the substituent group is preferably a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms.
  • (Z 11 ) - represents a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a carboxylate ion and a sulfonate ion, preferably a perchlorate ion, a hexafluorophosphate ion, a carboxylate ion and an aryl sulfonate ion.
  • other polymerization initiators can be used than the sulfonium salt polymerization initiator.
  • the other radical generating agents include onium salts (excluding sulfonium salts), triazine compounds having a trihalomethyl group, peroxides, azo-type polymerization initiators, azide compounds, quinone diazide, activated halogen compounds, oxime ester compounds and triaryl monoalkyl borate compounds.
  • the onium salts are highly sensitive and preferably used.
  • onium salts which can be used preferably in the present invention include iodonium salts and diazonium salts. In the present invention, these onium salts function not as acid generating agents but as radical polymerization initiators.
  • Examples of the onium salts used preferably in the present invention include onium salts represented by the formulae (2) and (3).
  • Formula (2) Ar 21 ⁇ I + ⁇ Ar 22 (Z 21 ) - Formula (3) Ar 31 ⁇ N + ⁇ N (Z 31 ) -
  • Ar 21 and Ar 22 each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent group.
  • the substituent group is preferably a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms.
  • (Z 21 ) - represents a counter ion having the same meaning as defined for (Z 11 ) - .
  • Ar 31 represents an aryl group having 20 or less carbon atoms, which may have a substituent group.
  • the substituent group is preferably a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms or an aryloxy group having 12 or less carbon atoms, an alkylamino group having 12 or less carbon atoms, a dialkylamino group having 12 carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms.
  • (Z 31 ) - represents a counter ion having the same meaning as defined for (Z 11 ) - .
  • examples of the onium salts preferably used as the polymerization initiator (radical generating agent) include those described in JP-A No. 2001-133696 .
  • the polymerization initiator (radical-generating agent) used in the present invention has a maximum absorption wavelength of preferably 400 nm or less, more preferably 360 nm or less.
  • the radical-generating agent having its absorption wavelength in the UV range, the planographic printing plate precursor can be handled under an incandescent lamp.
  • the total content of the polymerization initiator in the present invention is 0.1 to 50% by mass, and preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on a total solid content in the photosensitive layer.
  • only one polymerization initiator or two or more polymerization initiators may be used.
  • two or more polymerization initiators are used in combination, for example, two or more sulfonium salt polymerization initiators, which are preferably used, can be used, or the sulfonium salt polymerization initiator can be used in combination with another polymerization initiator.
  • the ratio (ratio by mass) of the sulfonium salt polymerization initiator to the other polymerization initiator is preferably 100/1 to 100/50, more preferably 100/5 to 100/25.
  • the polymerization initiator may be added to the same layer or to a separately provided layer.
  • a radial polymerization reaction proceeds efficiently to make the formed image very strong. Accordingly, a planographic printing plate having an oxygen-cutoff function obtained by the high protective layer which will be explained later and also high strength of an image area can be manufactured, with the result that printing durability is more improved. Also, because the sulfonium salt polymerization initiator is itself superior in stability with time, there is the advantage that the generation of an undesired polymerization reaction is suppressed efficiently when the manufactured planographic printing plate precursor is stored.
  • the polymerizable compound used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds each having at least one (preferably two or more) ethylenically unsaturated bond.
  • a group of such compounds is known widely in this industrial field, and in the present invention these compounds can be used without any particular limitation. These compounds occur in chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, as well as mixtures thereof and copolymers thereof.
  • Examples of such monomers and copolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters and amides thereof, and preferably used among these compounds are esters between unsaturated carboxylic acids and aliphatic polyvalent alcohol compounds and amides between unsaturated carboxylic acids and aliphatic polyvalent amine compounds.
  • unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.
  • esters and amides thereof are esters between unsaturated carboxylic acids and aliphatic polyvalent alcohol compounds and amides between unsaturated carboxylic acids and aliphatic polyvalent amine compounds.
  • unsaturated carboxylates having nucleophilic substituent groups such as hydroxyl group, amino group, mercapto group etc.
  • addition-reaction products of amides with monofunctional or multifunctional isocyanates or epoxy compounds and dehydration condensation reaction products of amides with monofunctional or multifunctional carboxylic acids.
  • unsaturated carboxylates having electrophilic substituent groups such as isocyanate group, epoxy group etc.
  • addition-reaction products of amides with monofunctional or multifunctional alcohols, amines or thiols unsaturated carboxylates having eliminating substituent groups such as halogen group, tosyloxy group etc.
  • substitution-reaction products of amides with monofunctional or multifunctional alcohols, amines or thiols can also be used.
  • the acrylates include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butane diol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri(acryloyloxypropyl)ether, trimethylol ethane triacrylate, hexane diol diacrylate, 1,4-cyclohexane diol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, dipentaerythritol diacrylate, dipentaerythritol hexacrylate, sorbitol triacrylate, sorbitol triacrylate, sorbitol triacrylate, sorbitol triacrylate, sorb
  • the methacrylates include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butane diol dimethacrylate, hexane diol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethyl methane, bis[p-(methacryloxyeth
  • the itaconates include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butane diol diitaconate, 1,4-butane diol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate etc.
  • the crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate etc.
  • the isocrotonates include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate etc.
  • the maleates include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate etc.
  • esters include, for example, aliphatic alcohol-based esters described in Japanese Patent Application Publication ( JP-B) Nos. 46-27926 , 51-47334 and Japanese Patent Application Laid-Open ( JP-A) No. 57-196231 , those having an aromatic skeleton described in JP-A Nos. 59-5240 , 59-5241 and 2-226149 , and those having an amino group described in JP-A No. 1-165613 .
  • the ester monomers can also be used as a mixture.
  • the amide monomers between aliphatic polyvalent amine compounds and unsaturated carboxylic acids include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, diethylene triamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide etc.
  • Preferable examples of other amide type monomers include those having a cyclohexylene structure described in JP-B No. 54-21726 .
  • Urethane type addition-polymerizable compounds produced by addition reaction between isocyanates and hydroxyl groups are also preferable, and examples thereof includes vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule, which are prepared by adding vinyl monomers containing a hydroxyl group shown in the formula below to polyisocyanates compound having two or more isocyanate groups in one molecule as described in JP-B No. 48-41708 .
  • Formula CH 2 C(R a )COOCH 2 CH(R b )OH
  • R a and R b each independently represent H or CH 3 .
  • Urethane acrylates described in JP-A No. 51-37193 , JP-B Nos. 2-32293 and 2-16765 and urethane compounds having an ethylene oxide-type skeleton described in JP-B Nos. 58-49860 , 56-17654 , 62-39417 and 62-39418 are also preferable.
  • Addition-polymerizable compounds having an amino structure or sulfide structure in the molecule as described in JP-ANos. 63-277653 , 63-260909 and 1-105238 can be used to prepare photopolymerizable compositions extremely excellent in photosensitizing speed.
  • multifunctional acrylates and methacrylates such as polyacrylates and epoxy acrylates obtained by reacting epoxy resin with (meth)acrylic acid as described in JP-A No. 48-64183 , JP-B Nos. 49-43191 and 52-30490 can be mentioned.
  • Specific unsaturated compounds described in JP-B Nos. 46-43946 , 1-40337 and 1-40336 and vinyl phosphonic acid-type compounds described in JP-A No. 2-25493 can also be mentioned.
  • a structure containing a perfluoroalkyl group described in JP-A No. 61-22048 is preferably used.
  • Photo-curable monomers and oligomers described in the Journal of Japanese Adhesive Society, vol. 20, No. 7, pp.300-308 (1984) can also be used.
  • the additional-polymerizable compounds preferably have many unsaturated groups in one molecule, and in many cases, they are preferably bifunctional or more. In order to increase the strength of image areas, i.e. the cured layer, they are preferably trifunctional or more. It is also effective to use a method of regulating both photosensitivity and strength by combined use of compounds (e.g.
  • acrylates, methacrylates, styrene type compounds, and vinyl ether type compounds having different functionalities and different polymerizable groups.
  • the high-molecular compounds or highly hydrophobic compounds though being excellent in photosensitizing speed and film strength, may be undesirable in some cases in respect of developing speed and precipitation in the developing solution.
  • the method of selecting and using the addition-polymerizable compound is an important factor for compatibility and dispersibility with other components (e.g. a binder polymer, an initiator, a colorant etc.) in the photosensitive layer composition, and the compatibility may be improved by using e.g. a low-purity compound or a combination of two or more compounds.
  • a specific structure can be selected for the purpose of improving adhesiveness to a support, a protective layer, described later, etc.
  • the addition polymerizable compound is preferably used in an amount of 5 to 80% by mass and more preferably 40 to 75% by mass based on a total solid content in the photosensitive layer composition from the viewpoint of sensitivity, generation of phase separation, adhesion of the photosensitive layer and also precipitation characteristics from a developing solution.
  • These compounds may be used singly or in combination thereof.
  • a suitable structure, compounding and amount thereof can be arbitrarily selected in the method of using the addition-polymerizable compound.
  • a layer structure and a coating method such as undercoating and overcoating can also be used as necessary.
  • the photosensitive layer in the present invention preferably comprises a binder polymer, particularly preferably a binder polymer having a repeating unit represented by the formula (i).
  • the binder polymer having a repeating unit represented by the formula (i) is also referred to as "specific binder polymer" and described in more detail below.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a linking group containing two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom, and the total number of atoms in R 2 is 2 to 82
  • A represents an oxygen atom or -NR 3 - in which R 3 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms
  • n is an integer from 1 to 5.
  • R 1 in the formula (i) represents a hydrogen atom or a methyl group, preferably a methyl group.
  • the linking group represented by R 2 in the formula (i) is a linking group containing two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom, and the total number of atoms in R 2 is 2 to 82, preferably 2 to 50, and more preferably 2 to 30.
  • the total number of atoms refers to the number of atoms including atoms in a substituent group, if any, on the linking group.
  • the number of carbon atoms in the main skeleton of the linking group represented by R 2 is preferably 1 to 30, more preferably 3 to 25, still more preferably 4 to 20, and most preferably 5 to 10.
  • the "main skeleton of the linking group" in the present invention refers to an atom or an atomic group used in linking A to the terminal COOH in the formula (i), and when a plurality of linkages are present, the main skeleton refers to an atom or an atomic group constituting a linkage having the smallest number of atoms. Accordingly, when the linking group has a cyclic structure, its linking sites (for example, o-, m-, p-, etc.) are different in the number of atoms to be introduced into them.
  • linking group represented by R 2 include an alkylene group, a substituted alkylene group, an arylene group and a substituted arylene group, and these divalent groups may be in a chain structure bound to one another via amide or ester linkages.
  • Linking groups in the chain structure include ethylene, propylene, etc.
  • a structure comprising these alkylene groups bound to one another via ester linkages is also preferable.
  • the linking group represented by R 2 in formula (i) is preferably a (n+1)-valent hydrocarbon group having an alicyclic structure having 3 to 30 carbon atoms.
  • Examples thereof include (n+1)-valent hydrocarbon groups obtained by removing (n+1) hydrogen atoms on arbitrary carbon atoms constituting compounds having an alicyclic structure, such as cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tertiary cyclohexyl and norbornane which may be substituted with one or more arbitrary substituent groups.
  • R 2 is preferably the one containing 3 to 30 carbon atoms including carbon atoms in a substituent group if any.
  • R 2 is preferably a (n+1)-valent hydrocarbon group having an alicyclic structure which may have a substituent group having 5 to 30 carbon atoms comprising two or more rings, such as a condensed polycyclic aliphatic hydrocarbon, a crosslinked alicyclic hydrocarbon, spiroaliphatic hydrocarbon, and combined aliphatic hydrocarbon rings (plural rings combined directly or via linking groups).
  • the number of carbon atoms refers to the number of carbon atoms including carbon atoms in a substituent group, if any.
  • the linking group represented by R 2 is preferably a group containing 5 to 10 atoms constituting a main structure of the linking group, having a cyclic structure containing an ester linkage or the cyclic structure described above.
  • a substituent group which can be introduced into the linking group represented by R 2 includes a monovalent non-metal atomic group excluding hydrogen, and examples thereof include a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkyl thio group, aryl thio group, alkyl dithio group, aryl dithio group, amino group, N-alkyl amino group, N,N-dialkyl amino group, N-aryl amino group, N,N-diaryl amino group, N-alkyl-N-aryl amino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-aryl carbamoyloxy group, N,N-dialkyl carbamoyloxy group, N,N-diaryl carbamoyloxy group, N-alkyl-N-aryl carbamoyloxy
  • a substituent group having a hydrogen atom capable of hydrogen bonding particularly a substituent group having acidity whose acid dissociation constant (pKa) is lower than that of carboxylic acid, is not preferable because it tends to deteriorate printing durability.
  • a hydrophobic substituent group such as a halogen atom, a hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group), an alkoxy group and an aryloxy group is preferable because it tends to improve printing durability, and particularly when the cyclic structure is a 6- or less memberred monocyclic aliphatic hydrocarbon such as cyclopentane or cyclohexane, the hydrocarbon preferably has such hydrophobic substituent groups. If possible, these substituent groups may be bound to one another or to a substituted hydrocarbon group to form a ring, and the substituent groups may further be substituted.
  • R 3 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 3 includes an alkyl group, aryl group, alkenyl group and alkynyl group.
  • alkyl group examples include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamanthyl group and 2-norbomyl group.
  • a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as a methyl group, ethyl group, propyl group,
  • aryl group examples include an aryl group having 6 to 10 carbon atoms such as a phenyl group, naphthyl group and indenyl group, and a heteroaryl group having 5 to 10 carbon atoms containing one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, for example a furyl group, thienyl group, pyrrolyl group, pyridyl group and quinolyl group.
  • alkenyl group examples include a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms such as a vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group and 1-cyclohexenyl group.
  • alkynyl group examples include an alkynyl group having 2 to 10 carbon atoms such as an ethynyl group, 1-propynyl group, 1-butynyl group and 1-octynyl group.
  • Substituent groups which may be possessed by R 3 include the same substituent groups as those capable of being introduced into R 2 .
  • the number of carbon atoms in R 3 including the number of carbon atoms in its substituent group, is 1 to 10.
  • a in the formula (i) is preferably an oxygen atom or ⁇ NH ⁇ because of easy synthesis.
  • n in the formula (i) is an integer from 1 to 5, preferably 1 in view of printing durability.
  • repeating unit represented by the formula (i) in the specific binder polymer are shown below, but the present invention is not limited thereto.
  • One or two or more kinds of repeating unit represented by the formula (i) may be contained in the binder polymer.
  • the specific binder polymer in the present invention may be a polymer composed exclusively of the repeating unit represented by the formula (i), but is usually used as a copolymer containing other copolymerizable components.
  • the total content of the repeating unit represented by the formula (i) in the copolymer is suitably determined depending on the structure of the copolymer, design of the photosensitive layer, etc., but usually the repeating unit represented by the formula (i) is contained in an amount of 1 to 99% by mole, more preferably 5 to 40% by mole, and still more preferably 5 to 20% by mole, based on the total molar amount of the polymer components.
  • copolymerizable components known in the art can be used without limitation insofar as they are radical-polymerizable monomers. Specifically, monomers described in the Polymer Data Handbook-Fundamental Version- compiled by the Society of Polymer Science, Japan and published by Baifukan, 1986 are exemplified. Such copolymerizable components can be used alone or in combination.
  • the molecular weight of the specific binder polymer in the present invention is suitably determined from the viewpoint of image-forming property and printing durability.
  • the molecular weight is preferably in the range of 2,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 200,000.
  • the specific binder polymer may be used alone, or may be used in combination with one or more other binder polymers.
  • binder polymers used in combination therewith are used in the range of 1 to 60% by mass, preferably 1 to 40% by mass, and more preferably 1 to 20% by mass, based on the total weight of the binder polymer components.
  • any known binder polymers can be used without limitation, and specifically an acrylic main-chain binder and an urethane binder used often in this field are preferably used.
  • the total amount of the specific binder polymer and binder polymers which can be used in combination therewith in the photosensitive layer composition can be suitably determined, and is usually 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, based on the total mass of nonvolatile components in the photosensitive composition.
  • the acid value (meg/g) of the binder polymer is preferably in the range of 2.00 to 3.60.
  • the binder polymer which can be used in combination with the specific binder polymer is preferably a binder polymer having a radical-polymerizable group.
  • the content of the radical-polymerizable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 1.0 to 7.0 mmol, and most preferably 2.0 to 5.5 mmol, per 1 g of the binder polymer from the viewpoint of sensitivity and storability.
  • the binder polymer further has an alkali-soluble group.
  • the content of the alkali-soluble group (acid value determined by neutralization titration) in the binder polymer is preferably 0.1 to 3.0 mmol, more preferably 0.2 to 2.0 mmol, and most preferably 0.45 to 1.0 mmol, per 1 g of the binder polymer, from the viewpoint of precipitation of development scum and printing durability.
  • the weight-average molecular weight of the binder polymer is in the range of preferably 2,000 to 1,000,000, more preferably 10,000 to 300,000, and most preferably 20,000 to 200,000, from the viewpoint of film property (printing durability) and solubility in a coating solvent.
  • the glass transition point (Tg) of the binder polymer is in the range of preferably 70° to 300°C, more preferably 80° to 250°C, and most preferably 90° to 200°C, from the viewpoint of storage stability, printing durability and sensitivity.
  • its molecule preferably contains an amide group or imide group, and particularly preferably contains methacrylamide derivatives.
  • Dyes or pigments may be added to the photosensitive layer of the present invention for the purpose of coloring.
  • the plate-checking property that is, the visibility of the printing plate after plate-making and the applicability for image densitometer can thereby be improved when the composition is applied to the printing plate.
  • the colorant include pigments such as phthalocyanine type pigments, azo type pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo type dyes, anthraquinone type dyes and cyanine type dyes.
  • cationic dyes are preferable.
  • the amount of the dyes and pigments added is preferably about 0.5 to about 5% by mass of nonvolatile components in the entire photosensitive layer composition.
  • a small amount of a heat-polymerization inhibitor is preferably added to the photosensitive layer of the present invention in order to inhibit undesired heat polymerization of the polymerizable compound having an ethylenically unsaturated double bond.
  • the heat-polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butyl phenol), 2,2'-methylene bis(4-methyl-6-t-butyl phenol), N-nitrosophenyl hydroxylamine primary cerium salts, etc.
  • the amount of the heat-polymerization inhibitor added is preferably about 0.01 to about 5% by mass relative to the mass of nonvolatile components in the entire composition.
  • a higher fatty acid derivative such as behenic acid or behenic amide may be added as necessary so that it is allowed to be locally present on the surface of the photosensitive layer in the drying step after application.
  • the amount of the higher fatty acid derivative added is preferably about 0.5 to about 10% by mass relative to nonvolatile components in the entire photosensitive layer composition.
  • additives such as inorganic fillers for improving the physical properties of the cured layer, as well as other plasticizers and sensitizers for improving inking properties on the surface of the photosensitive layer may also be added to the photosensitive layer of the invention.
  • the plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, etc., and these can be added in an amount of 10% by mass or less relative to the total mass of the binder polymer and the addition-polymerizable compound.
  • UV initiators and heat-crosslinking agents for enhancing the effect of heating and irradiation after development can also be added for the purpose of improving the layer strength (printing durability) described later.
  • an aluminium support which has been subjected to hydrophilization treatment described later is used.
  • An aluminum plate is better in dimensional stability, is relatively inexpensive, and can provide a surface excellent in hydrophilicity and a strength by optional surface treatment is further preferable.
  • a composite sheet in which an aluminum sheet is connected on a polyethylene terephthalate film described in JP-B No. 48-18327 is also preferable.
  • An aluminum plate as a support of the invention is a metal plate containing dimensionally stable aluminum as a main component, and is selected from, in addition to a pure aluminum plate, an alloy plate containing aluminum as a main component and a minor amount of heterogeneous element, and a plastic film or a paper on which aluminum (alloy) is laminated or deposited.
  • the aforementioned support consisting of aluminum or aluminum alloy, and the like, is collectively referred to as aluminum support for use.
  • a heterogeneous element contained in the aluminum alloy there are silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and a content of a heterogeneous element in an alloy is 10 % by mass or less.
  • a pure aluminum plate is preferable, but since completely pure aluminum is difficult to prepare from a viewpoint of refining technique, a heterogeneous element may be slightly contained.
  • an aluminum plate applied to the invention is not specified in its composition, but the previously known and used material, for example, JIS A 1050, JIS A 1100, JIS A 3103, and JIS A 3005 can be appropriately utilized.
  • the thickness of the aluminum support is about 0.1 to 0.6 mm. This thickness can be suitably changed depending on the size of a printing machine, the size of a printing plate, and user's demands.
  • the aluminum support may be subjected to support surface treatment described later and be hydrophilicity-conferred.
  • the surface roughening treatment includes mechanical roughening, chemical etching and electrolytic grain as disclosed in JP-A No. 56-28893 .
  • Use can also be made of an electrochemical surface roughening method for electrochemical surface roughening in a hydrochloric acid or nitric acid electrolyte and mechanical surface roughening methods such as a wire blush grain method of scratching an aluminum surface with a metallic wire, a pole grain method of graining an aluminum surface with abrasive grains ball and an abrasive and a brush grain method of surface roughening with a nylon brush and an abrasive, and these surface roughening methods can be used singly or in combination thereof.
  • the electrochemical method of chemical surface roughening in a hydrochloric acid or nitric acid electrolyte is particularly useful in surface roughening, and the suitable anodizing electrical quantity is in the range of 50 to 400 C/dm 2 .
  • alternating current and/or direct current electrolysis is conducted preferably at a temperature of 20 to 80°C, for 1 second to 30 minutes and at a current density of 100 to 400 C/dm 2 in an electrolyte containing 0.1 to 50% hydrochloric acid or nitric acid.
  • the aluminum support thus surface-roughened may be etched chemically with an acid or an alkali.
  • the etching agent include sodium hydroxide, sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, potassium hydroxide, lithium hydroxide etc., and the concentration and temperature are preferably in the range of 1 to 50% and 20 to 100°C, respectively.
  • washing with an acid is carried out to remove smuts remaining on the surface.
  • the acid used includes nitric acid, sulfuric acid, phosphoric acid, chromic acid, fluoric acid and borofluoric acid.
  • the method of removing smuts is preferably a method of contacting with sulfuric acid of 15 to 65% by mass at a temperature of 50 to 90°C as described in JP-A No. 53-12739 and a method of alkali etching as described in JP-B No. 48-28123 .
  • the method and conditions are not limited insofar as the central line average roughness Ra of the treated surface after the above-described treatment is 0.2 to 0.5 ⁇ m.
  • the thus treated aluminum support having an oxide layer formed thereon is then subjected to anodizing treatment.
  • an aqueous solution of sulfuric acid, phosphoric acid, oxalic acid and/or boric acid-sodium borate can be used as the major component in an electrolytic bath.
  • the electrolyte may contain at least components usually contained in an Al alloy plate, electrode, tap water and underground water. Second and third components may also be contained.
  • the second and third components include, for example, metal ions such as Na, K, Mg, Li, Ca, Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, ammonium ions, and anions such as nitrate ion, carbonate ion, chlorine ion, phosphate ion, fluorine ion, sulfite ion, titanate ion, silicate ion and borate ion, and these may be contained at a concentration of 0 to 10000 ppm.
  • the plate is treated preferably with 30 to 500 g/L solution at a temperature of 10 to 70°C by direct current or alternating current electrolyte in the range of a current density of 0.1 to 40 A/m 2 .
  • the thickness of the anodized layer formed is in the range of 0.5 to 1.5 ⁇ m. Preferably, the thickness is in the range of 0.5 to 1.0 ⁇ m.
  • the treatment conditions should be selected such that the pore diameter of micropores present in the anodized layer formed on the support by the treatment described above is 5 to 10 nm and the pore density is 8 ⁇ 10 15 to 2 ⁇ 10 16 pores/m 2 .
  • the treatment is particularly preferably hydrophilicity-conferring treatment with silicate or polyvinylphosphonic acid.
  • the layer is formed from an Si or P element in an amount of 2 to 40 mg/m 2 , preferably 4 to 30 mg/m 2 .
  • the coating amount can be measured by fluorescence X ray analysis.
  • the aluminum support having an anodized layer formed thereon is dipped in an aqueous solution at pH 10 to 13 (determined at 25°C) containing an alkali metal silicate or polyvinylphosphonic acid in an amount of 1 to 30% by mass, more preferably 2 to 15% by mass, for example at 15 to 80°C for 0.5 to 120 seconds.
  • alkali metal silicate used in the hydrophilicization treatment sodium silicate, potassium silicate, lithium silicate etc. are used.
  • the hydroxide used for raising the pH value of the aqueous alkali metal silicate solution includes sodium hydroxide, potassium hydroxide, lithium hydroxide etc.
  • Alkaline earth metal salts or the group IVB metal salts may be incorporated into the treating solution described above.
  • the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate and barium nitrate, and water-soluble salts such as sulfate, hydrochloride, phosphate, acetate, oxalate and borate.
  • the group IVB metal salts include titanium tetrachloride, titanium trichloride, titanium potassium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride oxide, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride, etc.
  • the alkaline earth metal salts or the group IVB metal salts can be used singly or in combination thereof.
  • the amount of these metal salts is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass.
  • Silicate electrodeposition as described in US Patent No. 3,658,662 is also effective.
  • a support subjected to electrolytic grain as disclosed in JP-B No. 46-27481 , JP-A Nos. 52-58602 and 52-30503 , and surface treatment comprising the anodizing treatment in combination with the hydrophilicity-conferring treatment, are also useful.
  • planographic printing plate precursor of the invention is produced by disposing the photosensitive layer and the protective layer in this order and, as required, an undercoat layer on a support.
  • Such a planographic printing plate precursor may be produced by dissolving each coating solution containing the above various components in a proper solvent and by applying the obtained coating solutions one by one to a support.
  • the components for the photosensitive layer is dissolved in various organic solvents to obtain a photosensitive layer coating solution, and the coating solution is applied onto the support or the intermediate layer.
  • the solvent used includes acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetyl acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxy propanol, methoxy methoxy ethanol, di
  • the coating amount of the photosensitive layer mainly affects the sensitivity and developability of the photosensitive layer and the strength and printing durability of the layer exposed to light, and is desirably selected depending on the use. When the coating amount is too low, the printing durability is not sufficient. It is not preferable for the coating amount to be too high because sensitivity is reduced, light exposure requires more time, and a longer time is necessary for development processing.
  • the coating amount on the planographic printing plate precursor for scanning light exposure as the major object of the present invention is preferably in the range of about 0.1 to 10 g/m 2 , and more preferably 0.5 to 5 g/m 2 , in terms of dried weight.
  • an intermediate layer (undercoating layer) may be disposed between a photosensitive layer and a support for the purpose of improving adherability and contaminating property.
  • Specific examples of such the intermediate layer include those described in JP-B No. 50-7481 , JP-A No. 54-72104 , JP-A No. 59-101651 , JP-A No. 60-149491 , JP-A No. 60-232998 , JP-A No. 3-56177 , JP-A No. 4-282637 , JP-A No. 5-16558 , JP-A No. 5-246171 , JP-A No. 7-159983 , JP-A No.
  • a method of making the planographic printing plate of the invention comprises setting a stack in which a plurality of the planographic printing plate precursors of the invention are stacked while a protective layer and a back of an aluminum support are directly contacted, in a plate setter, automatically conveying one by one of the planographic printing plate precursors, subjecting the planographic printing plate precursors to exposing treatment at a wavelength of 750 nm to 1400 nm, and performing developing treatment under condition of a conveying rate of 1.25 m/min or more substantially without via heat treatment.
  • planographic printing plate precursor of the invention can be applied to the aforementioned plate-making method because adherability between planographic printing plate precursors, and occurrence of a flaw on a protective layer are suppressed even when precursors are stacked without holding a set-off sheet therebetween.
  • planographic printing plate of the invention since a stack in which planographic printing plate precursors are stacked without holding a set-off sheet therebetween is used, it becomes unnecessary to remove a set-off sheet, and productivity in a plate-making step is improved.
  • this plate-making method is also preferable for plate making of the planographic printing plate precursor of the invention, and can be preferably applied to all of planographic printing plate precursors provided with a polymerizable negative-type photosensitive layer containing at least an infrared absorbing agent, a polymerization initiator and a polymerizable compound, and having solubility in an alkali developer which is reduced by exposure to a wavelength of 750 nm to 1400 nm.
  • a photosensitive layer may be a photosensitive layer containing respective components of "infrared absorbing agent, polymerization initiator, and polymerizable compound" explained in item of respective components constituting a photosensitive layer of the planographic printing plate precursor of the invention, and may or may not contain the known binder polymer.
  • a photosensitive layer to which the method of making a planographic printing plate of the invention is applied has physical property of a developing rate at an unexposed part for an alkali developer having a pH of 10 to 13.5, of 80 nm/sec or more, and a permeating rate at an exposed part of the alkali developer, of 50 nF/sec or less.
  • a method of measuring this developing rate at an unexposed part of a photosensitive layer and a permeating rate of an alkali developer into a photosensitive layer after curing a method described in Japanese Patent Application No. 2004-248535 which was previously filed by the present applicant can be used.
  • Control of a developing rate at an unexposed part of a photosensitive layer and a permeating rate of an alkali developer into a photosensitive layer after curing can be performed by a conventional method, and a representative method is a method of using the aforementioned particular binder polymer and, additionally, for improving a developing rate at an unexposed part, addition of a hydrophilic compound is useful and, for suppressing permeation of a developer into an exposed part, addition of a hydrophobic compound is useful.
  • any light source can be used as the light source used in the light exposure, insofar as it can emit light at a wavelength of 750 nm to 1400 nm.
  • Preferable examples thereof include an IR laser.
  • the planographic printing plate precursor of the present invention is preferably imagewizely exposed with infrared ray having a wavelength of 750 nm to 1400 nm emitted by a solid laser or a semiconductor laser.
  • the output power of the laser is preferably 100 mW or more, and a multi-beam laser device is preferably used to reduce the light exposure time.
  • the light exposure time per pixel is preferably within 20 ⁇ sec.
  • the energy irradiated on the planographic printing plate precursor is preferably 10 to 300 mJ/cm 2 . When the energy for light exposure is too low, the curing of the photosensitive layer does not sufficiently proceed. When the energy for light exposure is too high, the photosensitive layer may be ablated with the laser to damage the image.
  • the light exposure method in the invention can be carried out by overlapping beams from a light source.
  • overlapping means that the distance between beam centers in the sub-scanning direction is smaller than the beam diameter.
  • the beam diameter is expressed in terms of full-width half-maximum (FWHM)
  • the overlapping can be quantitatively expressed as FWHM/distance between beam centers in the sub-scanning direction (i.e., overlapping coefficient).
  • the overlapping coefficient in the present invention is preferably 0.1 or more.
  • the scanning system using a light source in the light exposure device of the present invention is not particularly limited, and known scanning methods such as a drum outer surface scanning method, a drum inner surface scanning method or a flatbed scanning method can be used.
  • the channel of the light source may be single or multi-channel, but in the case of the drum outer surface scanning method, a multi-channel is preferably used.
  • the exposed planographic printing plate precursor is subjected to development treatment without carrying out any particular heat treatment and water-washing treatment as mentioned above.
  • No practice of this heat treatment enables suppression of image non-uniformity caused by the heat treatment.
  • no practice of these heat treatment and water-washing treatment enables stable high-speed treatment in development treatment.
  • a non-image part of a photosensitive layer is removed using a developer.
  • a developer used in the invention is preferably an alkali aqueous solution having a pH of 14 or less, and preferably contains an aromatic anionic surfactant.
  • An aromatic anionic surfactant used in a developer of the planographic printing plate precursor of the invention has the development promoting effect, and the effect of stabilizing dispersion of polymerizable negative-type photosensitive layer components and protective layer components in a developer, and this is preferable in stabilizing developing treatment.
  • an aromatic anionic surfactant used in the planographic printing plate precursor of the invention is a compound represented by the following formula (A) or the formula (B).
  • R 1 and R 3 each represent independently a straight or branched alkylene group of a carbon number of 1 to 5, specifically, examples include an ethylene group, a propylene group, a butylene group, and a pentylene group and, inter alia, an ethylene group and a propylene group are particularly preferable.
  • n and n each represent independently an integer selected from 1 to 100 and, inter alia, 1 to 30 is preferable, and 2 to 20 is more preferable.
  • m is 2 or more, plural R 1 s may be the same or different.
  • n is 2 or more, plural R 3 s may be the same or different.
  • t and u each represent independently 0 or 1.
  • R 2 and R 4 each represent independently a straight or branched alkyl group of a carbon number of 1 to 20, examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a dodecyl group and, inter alia, a methyl group, an ethyl group, an iso-propyl group, a n-propyl group, a n-butyl group, an iso-butyl group, and a tert-butyl group are particularly preferable.
  • p and q each represent an integer selected from 0 to 2.
  • Y 1 and Y 2 each represent a single bond or an alkylene group of a carbon number of 1 to 10, specifically, a single bond, a methylene group and an ethylene group are preferable, and a single bond is particularly preferable.
  • (Z 1 ) r+ and (Z 2 ) s+ each represent independently an alkali metal ion, an alkaline earth metal ion, or an ammonium ion which is substituted or not substituted with an alkyl group, examples include a lithium ion, a sodium ion, a potassium ion, a magnesium ion, a calcium ion, an ammonium ion, and a secondary to quaternary ammonium ion substituted with an alkyl group, an aryl group or an aralkyl group in a range of a carbon number of 1 to 20 and, particularly, a sodium ion is preferable.
  • r and s each represent 1 or 2.
  • aromatic anionic surfactants may be used either independently or in combinations of two or more.
  • the amount of the aromatic anionic surfactant it is effective to design the amount of the surfactant to be preferably in a range from 1.0 to 10% by mass and more preferably in a range from 2 to 10% by mass.
  • the content of the surfactant is less than 1.0% by mass, this brings about reductions in developing characteristics and the solubility of the photosensitive layer component. If the content is 10% by mass or more, the printing durability of the printing plate is reduced.
  • the developing solution according to the invention may use, in addition to the above aromatic anionic surfactant, other surfactants together.
  • other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene naphthyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan alkyl esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate and sorbitan trioleate and monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate.
  • the content of these other surfactants in the developing solution is 0.1 to 10% by mass based on the amount of effective components.
  • the developing solution according to the invention is preferably made to contain a chelating agent for a divalent metal with the intention to suppress the influences of, for example, calcium ions contained in hard water.
  • a chelating agent for a divalent metal include polyphosphates such as Na 2 P 2 O 7 , Na 5 P 3 O 3 , Na 3 P 3 O 9 , Na 2 O 4 P (NaO 3 P)PO 3 Na 2 and Calgon (sodium polymethaphosphate); aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and its potassium salts, sodium salts and amine salts, diethylenetriaminepentaacetic acid and its potassium salts and sodium salts, triethylenetetraminehexaacetic acid and its potassium salts and sodium salts, hydroxyethylethylenediaminetriacetic acid and its potassium salts and sodium salts, nitrilotriacetic acid and its potassium salts and sodium salts, 1,2-diaminocyclohexanet
  • ethylenediaminetetraacetic acid and its potassium salts sodium salts and amine salts, ethylenediaminetetra(methylenephosphonic acid) and its ammonium salts and potassium salts; and hexamethylenediaminetetra(methylenephosphonic acid) and its ammonium salts and potassium salts are preferable.
  • the optimum amount of the chelating agent varies corresponding to the hardness and amount of hard water to be used.
  • the chelating agent is contained in an amount of generally 0.01 to 5% by mass and preferably 0.01 to 0.5% by mass in the developing solution during use.
  • alkali metal salts of organic acids or inorganic acids may be added as developing regulators to the developing solution according to the invention.
  • sodium carbonate, potassium carbonate, ammonium carbonate, sodium citrate, potassium citrate and ammonium citrate may be used singly or in combinations of two or more.
  • alkali agent used in the developing solution according to the invention examples include inorganic alkali agents such as sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, potassium hydroxide, ammonium hydroxide and lithium hydroxide and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and tetramethylammoniumhydroxide. In the invention, these compounds may be used either singly or in combinations of two or more.
  • alkali agents other than the above agents may include alkali silicates. These alkali silicates may be used in combination with a base. Examples of the alkali silicates to be used are those exhibiting alkalinity when dissolved in water and include sodium silicate, potassium silicate, lithium silicate and ammonium silicate. These silicates may be used either singly or in combinations of two or more.
  • the developing solution used in the invention may be easily adjusted to an optimum range by controlling the mixing ratio of silicon oxide SiO 2 which is a component of silicate (silicate is a component to impart hydrophilicity to the support) to an alkali oxide M 2 O (M represents an alkali metal or an ammonium group) which is an alkali component, and the concentrations of these components.
  • the mixing ratio (molar ratio of SiO 2 /M 2 O) of silicon oxide SiO 2 to an alkali oxide M 2 O is preferably in a range from 0.75 to 4.0 and more preferably in a range from 0.75 to 3.5 from the viewpoint of suppressing the occurrence of stains caused by excess dissolution (etching) of an anodic oxide film of the support and generation of insoluble gas caused by the formation of a complex of dissolved aluminum and a silicate.
  • the concentration of the alkali silicate in a developing solution is preferably in a range from 0.01 to 1 mol/L and more preferably in a range from 0.05 to 0.8 mol/L as the amount of SiO 2 based on the mass of the developing solution from the viewpoint of the effect of suppressing dissolution (etching) of an anodic oxide film of the support, developing ability, the effect of suppressing precipitation and generation of crystals and the effect of preventing gelation when developing solution waste is neutralized.
  • the developing solution used in the invention may use the following components together according to the need besides the above components.
  • these components include organic carboxylic acids such as benzoic acid, phthalic acid, p-ethylbenzoic acid, p-n-propylbenzoic acid, p-isopropylbenzoic acid, p-n-butylbenzoic acid, p-t-butylbenzoic acid, p-2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid and 3-hydroxy-2-naphthoic acid; organic solvents such as propylene glycol; and others including reducing agents, dyes, pigments, water softeners and antiseptics.
  • the developing solution used in the invention has a pH in a range from preferably 10 to 12.5 and more preferably 11 to 12.5 at 25°C. Since the developing solution of the invention contains the aforementioned surfactant, excellent developing characteristics are developed in the non-image arae even if a developing solution having such low pH is used. Such a measures as to make the developing solution have a lower pH reduces damages to the image area during developing and improves the handling characteristics of the developing solution.
  • the conductivity x of the developing solution preferably satisfies the equation 2 ⁇ x ⁇ 30 mS/cm and is more preferably 5 to 25 mS/cm.
  • alkali metal salts of organic acids or inorganic acids as conductive regulators that regulate conductivity.
  • the above developing solution may be used as a developing solution for an exposed planographic printing plate precursor and as a developing replenishing solution and is preferably applied to an automatic developing machine.
  • the developing solution is exhausted corresponding to the throughput and a replenishing or fresh developing solution may be therefore used to recover developing capability.
  • This replenishing system is also preferably applied in the plate-making method of the invention.
  • a more preferable development replenisher in the invention is a development replenisher characterized in that it contains an oxycarboxylic acid chelating agent having a water-soluble chelate compound forming ability with an aluminum ion, alkali metal hydroxide, and a surfactant, does not contain silicate, and is an aqueous solution having a pH of 11 to 13.5.
  • such the property is possessed that excellent developability and a strength of an image part of a printing material are not deteriorated, precipitation of aluminum hydroxide formed by dissolution of an aluminum support by an alkali of a developer is effectively suppressed, adhesion of a stain having aluminum hydroxide as a main component onto a surface of a developing bath roller of an automatic developing machine and, subsequently, accumulation of aluminum hydroxide precipitate in a water washing bath are reduced, and treatment can be stably performed for a long period of time.
  • planographic printing plate precursor developed in this manner is subjected to after-treatment performed using rinsing water, a rinsing solution containing surfactants and the like and a protective gum solution containing gum arabic and a starch derivative as its major components.
  • these treatments are used in various combinations.
  • the planographic printing plate obtained by such treatments is placed in an offset printer and used for printing a number of copies.
  • the developed image may be subjected to after-heating treatment and exposure performed on the entire surface for the purpose of improving image strength and printing durability.
  • Very strong conditions can be utilized in the heating after the image is developed.
  • the heating is usually carried out at a temperature in a range from 200 to 500°C. If the heating temperature after the development treatment is too low, only an insufficient image strengthening effect is obtained whereas if the heating temperature is too high, there are fears of a deterioration of the support and thermal decomposition of the image area.
  • planographic printing plate obtained by such treatments is placed in an offset printer and used for printing a number of copies.
  • the plate cleaner used to remove stains on the plate during printing a conventionally known plate cleaner for PS plate is used.
  • the plate cleaner include CL-1, CL-2, CP, CN-4, CN, CG-1, PC-1, SR and IC (manufactured by Fuji Photo Film Co., Ltd.).
  • a 0.30-mm-thick and 1030-mm-wide JIS A1050 aluminum plate was used to carry out the following surface treatment
  • the surface roughness Ra of the aluminum support obtained in this manner was 0.27 (measuring device: SURFCOM, manufactured by TOKYO SEIMITSU Co., Ltd., diameter of the tracer head: 2 m ⁇ ).
  • undercoat layer coating solution was applied to this aluminum support by using a wire bar and dried at 90°C for 30 minutes.
  • the amount applied was 10 mg/m 2 .
  • the following photosensitive layer coating solution [P-1] was prepared, and coated on the aluminum support described above using a wire bar. Drying was performed with a warm air drying device at 115°C for 34 seconds to obtain a planographic printing plate precursor. A covering amount after drying was 1.4 g/m 2 .
  • IR-1 IR-1 0.074 g ⁇ Polymerization initiator (OS-12) 0.280 g ⁇ Additive (PM-1) 0.151 g ⁇ Polymerizable compound (AM-1) 1.00 g ⁇ Particular binder polymer (BT-1) 1.00 g ⁇ Ethyl violet (C-1) 0.04 g ⁇ Fluorine-based surfactant 0.015 g (trade name MEGAFACK F-780-F, manufactured by Dainippon Ink and Chemicals, Incorporated, 30 mass% solution in methyl isobutyl ketone (MIBK)) ⁇ Methyl ethyl ketone 10.4 g ⁇ Methanol 4.83 g ⁇ 1-Methoxy-2-propanol 10.4 g
  • MIBK methyl isobutyl ketone
  • the polymerization initiator (OS-12) used in the aforementioned photosensitive layer coating solution refers to a polymerization initiator listed as a compound example of an onium salt represented by the formula (1). Structures of the infrared absorbing agent (IR-1), the additive (PM-1), the polymerizable compound (AM-1), the binder polymer (BT-1), and the ethyl violet (C-1) are shown below.
  • a mixed aqueous solution (coating solution for protective layer) of specified polyvinyl alcohol having a saponification degree of 91 mol% or more (trade name: PVA-105, manufactured by Kuraray Co., Ltd.: saponification degree 98.5 mol%, polymerization degree 500), Pluronic P-84 (manufactured by ADEKA CORPORATION, ethylene oxide/propylene oxide copolymer) and a surfactant (trade name EMULLEX 710, manufactured by Nihon-emulsion Co., Ltd.) was coated on a surface of the photosensitive layer with a wire bar, and dried with a warm air drying device at 125°C for 75 seconds to prepare a protective layer.
  • PVA-105 manufactured by Kuraray Co., Ltd.: saponification degree 98.5 mol%, polymerization degree 500
  • Pluronic P-84 manufactured by ADEKA CORPORATION, ethylene oxide/propylene oxide copolymer
  • a surfactant trade name EMUL
  • a content ratio of specified polyvinyl alcohol/Pluronic P-84/surfactant in this mixed aqueous solution was 92/6/2 (% by mass), and a total coating amount (covering amount after drying) was 1.6 g/m 2 .
  • Oxygen permeability of this protective layer at 25°C, 60 %RH and 1 atm was measured, and found to be 10.7 ml/m 2 ⁇ day.
  • an oxygen shielding layer was coated on an about 200 ⁇ m photographic paper, on both sides of which were coated with about 20 ⁇ m polyethylene, as in coating on a photosensitive layer, and this was dried to prepare a sample for measuring oxygen permeability. Since oxygen permeability of a photographic paper is about 700 ml/m 2 ⁇ day ⁇ atm under the following condition, this can be sufficiently neglected in measuring an oxygen shielding layer.
  • the sample was measured for oxygen permeability ml/(m 2 ⁇ day ⁇ atm) under condition of 25°C and 60 %RH using OX-TRAN2/20 manufactured by Mocon.
  • Example 2 According to the same manner as that of Example 1 except that a kind and an addition amount of ethylene oxide/propylene oxide copolymer, and a kind of a binder component (specified polyvinyl alcohol) were changed as in the following Table 1 in a composition of the mixed aqueous solution (coating solution for protective layer) of Example 1, planographic printing plate precursors of Examples 2 to 6 were obtained.
  • Example 1 According to the same manner as that of Example 1 except that a coating solution was changed to a coating solution to which an ethylene oxide/propylene oxide copolymer was not added in a mixed aqueous solution (coating solution for protective layer) of Example 1, the planographic printing plate precursor of Comparative Example 1 was obtained.
  • Example 2 According to the same manner as that of Example 1 except that 6.0 % by mass of polyvinylpyrrolidone (K-30) was added in place of a copolymer of ethylene oxide and propylene oxide in the mixed aqueous solution (coating solution for protective layer) of Example 1, the planographic printing plate precursor of Comparative Example 2 was obtained.
  • K-30 polyvinylpyrrolidone
  • NM-11 represents completely saponified-type polyvinyl alcohol (trade name GOSENOL NM-11, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
  • JF-05 represents completely saponified-type polyvinyl alcohol (manufactured by Japan Vam & Poval Co., Ltd.)
  • Pluronic P-84, L-64, P-85, and F-88 represent an ethylene oxide/propylene oxide copolymer (manufactured by ADEKA CORPORATION.)
  • PVP K-30 represents polyvinylpyrrolidone (manufactured by ISP (Japan) Ltd.).
  • the resulting planographic printing plate precursor was exposed to light at resolution of 2400 dpi, an external surface drum rotation number of 200 rpm, and in a range of output of 0 to 8 W with Trendsetter 800II Quantum manufactured by Creo by exchanging by 0.15 in terms of logE. Exposure was performed under condition of 25°C and 50 %RH. After exposure, heat treatment and water washing treatment were not performed, and developing treatment was performed at a conveying rate (line rate) of 2 m/min and a developing temperature of 30°C using an automatic developing machine (trade name LP-1310HII manufactured by Fuji Photo Film Co., Ltd.).
  • a 1:4 water-diluted solution of DH-N was used, as a developing replenisher, a 1:1.4 water-diluted solution of FCT-421 was used and, as a finisher, a 1:1 water-diluted solution of GN-2K manufactured by Fuji Photo Film Co., Ltd. was used.
  • a cyan concentration was measured with a Macbeth reflection densitometer RD-918 using a red filter equipped in the densitometer. A reciprocal of a necessary light exposure amount for obtaining 0.9 of a measured concentration was adopted as an index for a sensitivity.
  • assessment results letting a sensitivity of the planographic printing plate obtained in Example 1 to be 100, a sensitivity of other planographic printing plate was relatively assessed. As a value is larger, a sensitivity is more excellent.
  • the resulting planographic printing plate after plate-making treatment was used to perform printing employing a printing machine (trade name DIA I F-2, manufactured by Mitsubishi Heavy Industries, Ltd.), and inking property was assessed by printing numbers from initial printing until a better printed matter is obtained without faded image part ink density.
  • a printing ink GRAPH G(N) manufactured by Dainippon Ink and Chemicals, Incorporated was used.
  • dampening water IF MARK II manufactured by Fuji Photo Film Co., Ltd. was used. As the printing number until inking is smaller, inking property is more excellent.
  • planographic printing plate precursors (10 ⁇ 10 cm) were moisture-conditioned for 2 hours under the environment of 25°C and 75 %RH, and three precursors were successively stacked in the same direction in the state where they and set-off sheets were stacked alternately, to obtain a stack.
  • This stack was sealing-packaged with an A1 kraft paper, and this was allowed to stand for 5 days under the environment of 30°C in the state where a load of 4 kg was applied. Thereafter, the stack was assessed for the state of adhesion between a surface on a photosensitive layer side (protective layer surface) of a planographic printing plate precursor and an adjacent set-off sheet. Adhesion between the planographic printing plate precursor and the set-off sheet was organoleptically assessed by 1 to 5, 3 is a practically lower limit level, and 2 or less is a practically failure level.
  • the resulting planographic printing plate precursor was exposed under a UV-cut fluorescent lamp at an illuminance of 400 Lx for a constant time, and a time until occurrence of fog at a non-image part after developing treatment was compared.
  • fog occurrence is defined as a part having a higher concentration by 0.2 or more as compared with a reflection concentration at a non-image part which is not under safe light exposure.
  • planographic printing plate precursors of Example 1 to Example 6 that is, planographic printing plate precursors in which a protective layer containing a copolymer of ethylene oxide and propylene oxide is disposed on a polymerizable negative-type photosensitive layer have a high sensitivity, are also excellent in safe light suitability, further, are excellent in inking property and, even when they are placed under a high humidity, adhesion between planographic printing plate precursors is not observed.
  • planographic printing plate precursor of Comparative Example 1 not containing a copolymer of ethylene oxide and propylene oxide is excellent in a sensitivity, and adhesion between planographic printing plate precursors is not observed after it was placed under a high humidity, but the precursor is remarkably inferior in safe light suitability.
  • planographic printing plate precursor of Comparative Example 2 in which polyvinylpyrrolidone was added in place of a copolymer of ethylene oxide and propylene oxide, a sensitivity was excellent, and safe light suitability was better, but adhesion between a planographic printing plate precursor and a set-off sheet was remarkably inferior after the precursor was placed under a high humidity, and inking property was inferior as compared with planographic printing plate precursors manufactured in Examples 1 to 6.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Structural Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Architecture (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Ink Jet (AREA)
  • Formation Of Insulating Films (AREA)
  • Electroluminescent Light Sources (AREA)

Claims (4)

  1. Précurseur de plaque d'impression planographique dans lequel une couche photosensible et une couche de protection sont successivement stratifiées sur une surface d'un support en aluminium présentant de l'hydrophilicité, caractérisé en ce que la couche de protection contient un polymère de liaison, et un copolymère d'oxyde d'éthylène et d'oxyde de propylène,
    dans lequel le polymère de liaison contenu dans la couche de protection est un alcool polyvinylique ayant un degré de saponification de 91 % en mole ou davantage, dans lequel une teneur de l'alcool polyvinylique ayant un degré de saponification de 91 % en mole ou davantage est de 45 à 95 % en masse par rapport à la quantité totale de matière solide de la couche de protection, dans lequel la teneur du copolymère d'oxyde d'éthylène et d'oxyde de propylène contenus dans la couche de protection est de 2,0 à 15 % en masse par rapport à la quantité totale de matière solide de la couche de protection, et dans lequel une quantité de revêtement de la couche de protection est de 0,3 à 3,0 g/m2 et
    dans lequel la couche photosensible contient un agent absorbant l'infrarouge, un initiateur de polymérisation, un composé polymérisable, et un polymère de liaison.
  2. Précurseur de plaque d'impression planographique selon la revendication 1, dans lequel une teneur d'oxyde d'éthylène contenu dans le copolymère d'oxyde d'éthylène et d'oxyde de propylène contenus dans la couche de protection est de 30 à 80 % en masse.
  3. Précurseur de plaque d'impression planographique selon l'une quelconque des revendications 1 à 2, dans lequel la perméabilité à l'oxygène de la couche de protection dans l'environnement de 25 °C, 65 % HR et 1 atm est de 0,5 ml/m2 par jour à 100 ml/m2 par jour.
  4. Précurseur de plaque d'impression planographique selon la revendication 1 à 3, dans lequel le polymère de liaison contenu dans la couche photosensible est un polymère de liaison ayant une unité répétitive représentée par la formule (i) suivante :
    Figure imgb0113
     dans la formule (i), R1 représente un atome d'hydrogène ou un groupe méthyle, R2 représente un groupe d'attachement contenant 2 ou plusieurs atomes sélectionnés dans le groupe constitué par un atome de carbone, un atome d'hydrogène, un atome d'oxygène, un atome d'azote et un atome de soufre et ayant le nombre de ces atomes allant de 2 à 82, A représente un atome d'oxygène ou -NR3-, R3 représente un atome d'hydrogène ou un groupe hydrocarboné monovalent ayant un nombre de carbones de 1 à 10, et n représente un nombre entier de 1 à 5.
EP06020269A 2005-09-27 2006-09-27 Précurseur de plaque d'impression planographique Active EP1767994B1 (fr)

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JP2005279197A JP4619912B2 (ja) 2005-09-27 2005-09-27 平版印刷版原版、及びその製版方法

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JP4911455B2 (ja) * 2006-09-27 2012-04-04 富士フイルム株式会社 光重合型感光性平版印刷版原版
US8318405B2 (en) 2009-03-13 2012-11-27 Eastman Kodak Company Negative-working imageable elements with overcoat
JP5281445B2 (ja) * 2009-03-17 2013-09-04 三菱製紙株式会社 感光性平版印刷版材料
WO2019049786A1 (fr) * 2017-09-05 2019-03-14 東洋紡株式会社 Composition de résine photosensible pouvant être développée dans l'eau pour impression flexographique, et plaque originale en résine photosensible pour impression flexographique produite à partir de ladite composition

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JPH0456863A (ja) * 1990-06-22 1992-02-24 Fuji Photo Film Co Ltd 平版印刷版の製版方法
US5677108A (en) * 1995-04-28 1997-10-14 Polaroid Corporation On-press removable quenching overcoat for lithographic plates
JP3676517B2 (ja) * 1996-10-02 2005-07-27 富士写真フイルム株式会社 ネガ型感光材料
DE69722773T2 (de) * 1996-11-20 2004-06-17 Latran Technologies Llc, Waltham Schutzüberzug, nützlich zu erhöhung der widerstandsfahigkeit eines druckplattenvorläufers gegen umgebungsfeuchtigkeit
JP3936474B2 (ja) * 1997-08-12 2007-06-27 富士フイルム株式会社 ネガ型感光材料
JP2005107388A (ja) * 2003-10-01 2005-04-21 Fuji Photo Film Co Ltd 光重合性画像記録材料及びそれを用いた平版印刷版原版の製造方法
US20050153239A1 (en) * 2004-01-09 2005-07-14 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor and lithographic printing method using the same

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ATE466312T1 (de) 2010-05-15
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EP1767994A2 (fr) 2007-03-28
EP1767994A3 (fr) 2008-07-23
JP4619912B2 (ja) 2011-01-26

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